Substituted indoles

ABSTRACT

3-[(Alkoxy)(aryl or heteroaryl)methyl]-1H-indoles which are useful as color formers in pressure-sensitive carbonless duplicating systems and thermal marking systems are prepared by reacting 3-[(arylsulfonyl)(aryl or heteroaryl)methyl]-1H-indoles with alcohols in the presence of a base.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of copending application Ser. No. 288,495filed July 30, 1981, now U.S. Pat. No. 4,485,242 patented Nov. 27, 1984,in turn a division of application Ser. No. 127,648, filed Mar. 6, 1980,now U.S. Pat. No. 4,307,898 patented Dec. 29, 1981.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a group of compounds classified in thefield of organic chemistry as 3-[(alkoxy)(aryl orheteroaryl)methyl]-1H-indoles which are useful as colorformers inpressure-sensitive carbonless duplicating systems and thermal markingsystems; to processes for the preparation thereof and topressure-sensitive carbonless duplicating systems and thermal markingsystems containing the same.

2. Description of the Prior Art

Several classes of organic compounds of widely diverse structural typesare known to be useful as color formers for carbonless duplicatingsystems. Among the most widely recognized classes are thephenothiazines, for example, benzoyl leuco methylene blue; fluorans, forexample, 2'-anilino-6'-diethylaminofluoran; phthalides, for example,crystal violet lactone; methine dyes, for example, Michler's hydrol andderivatives thereof and various other types of color formers currentlyemployed in commercially accepted carbonless duplicating systems.Typical of the many such systems taught in the prior art are thosedescribed in U.S. Pat. Nos. 2,712,507, 2,800,457 and 3,041,289 whichissued July 5, 1955, July 23, 1957 and June 26, 1962, respectively. Manyof the color formers in the prior art suffer one or more disadvantagessuch as low tinctorial strength poor light stability, poor xerographiccopiability, low resistance to sublimation, and low solubility in commonorganic solvents, the latter disadvantage thus requiring the use ofspecialized and expensive solvents in order to obtain microencapsulatedsolutions of sufficient concentration for use in pressure-sensitivecopying systems.

The following appear to constitute the most relevant prior art relativeto the present invention.

U.S. Pat. No. 3,684,510, patented Aug. 15, 1972 discloses indolylmethanederivatives having the formula ##STR1## in which A is aryl or aheterocyclic aromatic group and R₁ and R₂ are hydrogen, alkyl oraralkyl. The compounds are stated to be useful in combination witharylamino compounds and tetrahalomethane compounds in light-sensitivematerials for the production of copies from an original.

U.S. Pat. No. 3,958,815 issued May 25, 1976 discloses in most pertinentpart a group of compounds stated to be useful as dye precursors inpressure-sensitive recording materials and having the formula ##STR2##wherein inter alia R₁ and R₂ represent (1) an aryl group substitutedwith an ether group R₆ --O-- in which R₆ represents a hydrocarbon groupor (2) a heterocyclic group; R₃ represents a --XH or --X--R₇ group inwhich X is oxygen or sulfur and R₇ is an organic group, and m and n are0.

French Pat. No. 1,561,663 published Mar. 28, 1969 discloses in mostpertinent part a series of compounds having the formula ##STR3## whereininter alia R₁ and R₂ are independently hydrogen, alkyl or aryl; B is acarbocyclic or heterocyclic ring system, and E is alkoxy. The compoundsare stated to be useful as intermediates in the preparation oftriphenylmethane dyes.

M. Scholtz, Chem. Ber. 46, 2138-2146 (1913) discloses a group of(phenyl, substituted-phenyl or furyl)(ethoxy ormethoxy)(α-methylindolyl)methanes prepared by reacting an appropriatebenzaldehyde or furfural with α-methylindole and ethanol or methanol inthe presence of a base. No utility is disclosed for these compounds.

SUMMARY OF THE INVENTION

The present invention provides certain novel 1-R₁ -2-R₂ -3-[(R₃O)(Z)methyl]-1H-indoles which are useful as color formers inpressure-sensitive carbonless duplicating systems and thermal markingsystems. The compounds develop colored images of good tinctorialstrength and have the advantage of good xerographic copiability andenhanced solubility in common organic solvents.

This invention also provides a novel process for preparing theabove-described novel 1-R₁ -2-R₂ -3-[(R₃ O)(Z)methyl]-1H-indoles as wellas certain known related compounds which comprises reacting a 1-R₁ -2-R₂-3-[(R-phenylsulfonyl)(Z)methyl]-1H-indole with an alcohol R₃ OH in thepresence of a base.

The invention further provides as an article of manufacture apressure-sensitive carbonless duplicating system or thermal markingsystem which contains a support sheet coated with a color-formingsubstance comprising a novel 1-R₁ -2-R₂ -3-[(R₃ O)(Z)methyl]-1H-indole

DETAILED DESCRIPTION OF THE INVENTION INCLUSIVE OF THE PREFERREDEMBODIMENTS

More specifically the invention sought to be patented resides in acomposition of matter aspect in 1-R₁ -2-R₂ -3-[(R₃O)(Z)methyl]-1H-indoles which are useful as color formers inpressure-sensitive duplicating systems and thermal marking systems andwhich have Formula I ##STR4## wherein: R₁ is hydrogen or lower-alkyl;

R₂ is hydrogen, lower-alkyl or phenyl;

R₃ is alkyl containing 1 to 8 carbon atoms,di-lower-alkylamino-lower-alkyl, tri-lower-alkylammonium-lower-alkyl,benzyl or benzyl substituted in the phenyl ring with 1 or 2 lower-alkylor lower-alkoxy groups, or a substituent having the formula ##STR5## andZ is biphenylyl, naphthyl or a substituent having the formula ##STR6##wherein R₄ and R₅ are independently lower-alkyl or benzyl, and

R₆ is hydrogen, lower-alkyl, lower-alkoxy, halo or di-lower-alkylamino.

In another composition of matter aspect the invention sought to bepatented resides in compounds of Formula I above useful as color formersin pressure-sensitive duplicating systems and thermal marking systems,wherein in said formula

R₁ and R₂ have the previously given meanings;

R₃ is di-lower-alkylamino-lower-alkyl ortri-lower-alkylammonium-lower-alkyl, and

Z is phenyl, tolyl or lower-alkoxy-phenyl.

A further composition of matter aspect of the invention sought to bepatented resides in a compound, useful as a color former inpressure-sensitive duplicating systems and thermal marking systems,selected from the group consisting of

3-[(4-methoxyphenyl)(4-methoxybenzyloxy)methyl]-2-methyl-1H-indole;

3-[(4-methoxyphenyl)(benzyloxy)methyl]-2-methyl-1H-indole;

3-[(3,4-dimethoxyphenyl)(methoxy)methyl]-2-methyl-1H-indole;

3-[(methoxy)(1-methyl-2-pyrrolyl)methyl]-1-ethyl-2-methyl-1H-indole;

3-[(9-ethyl-3-carbazolyl)(methoxy)methyl]-2-methyl-1H-indole; and

3-[(methoxy)(2-pyridyl)methyl]-2-methyl-1H-indole,

or the group consisting of

3-[(methoxy)(p-tolyl)methyl]-1H-indole;

3-[(methoxy)(4-methoxyphenyl)methyl]-1H-indole;

3-[(2-propoxy)(4-methoxyphenyl)methyl]-2-methyl-1H-indole;

3-[(n-butoxy)(4-methoxyphenyl)methyl]-2-methyl-1H-indole;

3-[(methoxy)(2-methoxyphenyl)methyl]-2-methyl-1H-indole;

3-[(3,4-dichlorophenyl)(methoxy)methyl]-2-methyl-1H-indole;

3-[(2-furyl)(methoxy)methyl]-1-ethyl-2-methyl-1H-indole;

3-[(methoxy)(2-thienyl)methyl]-1H-indole;

3-[(methoxy)(2-thienyl)methyl]-2-methyl-1H-indole;

3-[(methoxy)(2-thienyl)methyl]-1-ethyl-2-methyl-1H-indole;

3-[(n-butoxy)(2-thienyl)methyl]-2-methyl-1H-indole;

and

3-[(1-ethyl-2-methyl-1H-indol-3-yl)(methoxy)methyl]-1-ethyl-2-methyl-1H-indole.

Preferred embodiments of this invention are compounds of Formula Ihereinabove wherein R₁ and R₂ have the previously given meanings; R₃ isalkyl containing 1 to 8 carbon atoms or benzyl, and Z is a substituenthaving the formula ##STR7## where R₄ and R₅ have the previously givenmeanings and R₆ is hydrogen. These compounds are especially valuablebecause they are obtained from inexpensive and readily availablestarting materials.

In an article of manufacture aspect the invention sought to be patentedresides in a pressure-sensitive carbonless duplicating system or thermalmarking system containing a support sheet coated with a color-formingsubstance comprising a compound having Formula I hereinabove wherein

R₁ and R₂ have the previously given meanings;

R₃ is alkyl containing 1 to 8 carbon atoms,di-lower-alkylamino-lower-alkyl, tri-lower-alkylammonium-lower-alkyl,benzyl or benzyl-substituted in the phenyl ring with 1 or 2 lower-alkylor lowr-alkoxy groups, or a substituent having the formula ##STR8## andZ is biphenylyl, naphthyl or a substituent having the formula ##STR9##wherein R₄, R₅ and R₆ have the previously given definitions.

In another article of manufacture aspect the invention sought to bepatented resides in a pressure-sensitive carbonless duplicating systemor a thermal marking system containing a support sheet coated with acolor-forming substance comprising a compound having Formula Ihereinabove wherein:

R₁ and R₂ have the previously given meanings;

R₃ is di-lower-alkylamino-lower-alkyl ortri-lower-alkylammonium-lower-alkyl; and

Z is phenyl, tolyl or lower-alkoxyphenyl.

In yet a further article of manufacture aspect the invention sought tobe patented resides in a pressure-sensitive carbonless duplicatingsystem or a thermal marking system containing a support sheet coatedwith a color-forming substance comprising a compound selected from thegroup consisting of

3-[(4-methoxyphenyl)(4-methoxybenzyloxy)methyl]-2-methyl-1H-indole;

3-[(4-methoxyphenyl)(benzyloxy)methyl]-2-methyl-1H-indole;

3-[(3,4-dimethoxyphenyl)(methoxy)methyl]-2-methyl-1H-indole;

3-[(methoxy)(1-methyl-2-pyrrolyl)methyl]-1-ethyl-2-methyl-1H-indole;

3-[(9-ethyl-3-carbazolyl)(methoxy)methyl]-2-methyl-1H-indole; and

3-[(methoxy)(2-pyridyl)methyl]-2-methyl-1H-indole,

or the group consisting of

3-[(methoxy)(p-tolyl)methyl]-1H-indole;

3-[(methoxy)(4-methoxyphenyl)methyl]-1H-indole;

3-[(2-propoxy)(4-methoxyphenyl)methyl]-2-methyl-1H-indole;

3-[(n-butoxy)(4-methoxyphenyl)methyl]-2-methyl-1H-indole;

3-[(methoxy)(2-methoxyphenyl)methyl]-2-methyl-1H-indole;

3-[(3,4-dichlorophenyl)(methoxy)methyl]-2-methyl-1H-indole;

3-[(2-furyl)(methoxy)methyl]-1-ethyl-2-methyl-1H-indole;

3-[(methoxy)(2-thienyl)methyl]-1H-indole;

3-[(methoxy)(2-thienyl)methyl]-2-methyl-1H-indole;

3-[(methoxy)(2-thienyl)methyl]-1-ethyl-2-methyl-1H-indole;

3-[(n-butoxy)(2-thienyl)methyl]-2-methyl-1H-indole;

and

3-[(1-ethyl-2-methyl-1H-indol-3-yl)(methoxy)methyl]-1-ethyl-2-methyl-1H-indole.

Preferred pressure-sensitive carbonless duplicating systems or thermalmarking systems of the present invention are those which contain acolor-forming substance comprising a compound of Formula I wherein R₁and R₂ have the previously given meanings; R₃ is alkyl containing 1 to 8carbon atoms or benzyl; and Z is a substituent having the formula##STR10## where R₄ and R₅ have the above-given meanings and R₆ ishydrogen.

In its process aspect the invention sought to be patented resides in aprocess for producing a compound having Formula I which comprisesreacting a compound having Formula II ##STR11## with an alcohol havingFormula III

    R.sub.3 OH                                                 Formula III

in the presence of an alkali metal hydroxide or the alkali metal salt ofthe alcohol of Formula III wherein in said formulas

R is hydrogen or lower-alkyl;

R₁ and R₂ have the previously given definitions;

R₃ is alkyl containing 1 to 8 carbon atoms,di-lower-alkylamino-lower-alkyl, tri-lower-alkylammonium-lower-alkyl,benzyl or benzyl substituted in the phenyl ring with 1 or 2 lower-alkylor lower-alkoxy groups or a substituent having the formula ##STR12## andZ is lower-alkyl, biphenylyl, naphthyl, phenyl, phenyl substituted with1 or 2 lower-alkyl, lower-alkoxy, halo or nitro groups, or a substituenthaving the formula ##STR13## wherein R₄, R₅ and R₆ have the previouslygiven meanings and R₇ is hydrogen or lower-alkyl.

As used herein the terms "lower-alkyl", "lower-alkoxy" and"di-lower-alkylamino-" denote saturated acyclic groups having from 1 to4 carbon atoms which may be straight or branched as exemplified bymethyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl,methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy,t-butoxy, dimethylamino, diethylamino, ethylmethylamino, dipropylamino,dibutylamino, isobutylmethylamino, t-butylmethylamino and the like.

The term "alkyl containing 1 to 8 carbon atoms" denotes saturatedmonovalent straight or branched chain aliphatic hydrocarbon radicalsincluding methyl, ethyl, propyl, isopropyl, butyl, t-butyl, amyl,1-methylbutyl, 3-methylbutyl, hexyl, isohexyl, heptyl, isoheptyl, octyl,isooctyl, 2-ethylhexyl and the like.

The term "tri-lower-alkyl-ammonium-lower-alkyl" signifies anamino-lower-alkyl radical in which the nitrogen atom is substituted bythree sterically compatible lower-alkyl groups.

As used herein "tolyl" is intended to include ortho-, meta- andpara-tolyl; "halo" includes chloro, fluoro, bromo and iodo and "alkalimetal" includes lithium, sodium and potassium.

The novel compounds of Formula I hereinabove are essentially colorlessin the depicted form. When contacted with an acidic medium, for examplesilica gel or one of the types ordinarily employed in pressure-sensitivecarbonless duplicating systems such as silton clay or phenolic resin,the compounds of Formula I develop a yellow to deep purple image of goodto excellent tinctorial strength and possess excellent xerographiccopiability and enhanced solubility in common organic solvents. Thecompounds are thus highly suitable for use as colorless precursors, thatis, color-forming substances in pressure-sensitive carbonlessduplicating systems. Compounds producing darker purple colors can beused alone as color formers to produce images which are readily copiablewhereas the compounds which produce a yellow to red color can be used astoners in admixture with other color formers to produce images of aneutral shade which desirably are readily copiable by xerographic means.

The compounds of this invention can be incorporated in any of thecommercially accepted systems known in the carbonless duplicating art. Atypical technique for such application is as follows: solutionscontaining one or more colorless precursor compounds of Formula Ioptionally in admixture with other color formers in suitable solventsare microencapsulated by well-known procedures, for example as describedin U.S. Pat. Nos. 3,429,827, 3,649,649 and 4,000,087. The microcapsulesare coated on the reverse side of a transfer sheet with the aid of asuitable binder. The coated transfer sheet is then assembled in amanifold with the microcapsule-coated side in contact with a receivingsheet coated with an electronic accepting substance, for example siltonclay or phenolic resin. Application of pressure to the manifold such asthat exerted by a stylus, typewriter or other form of writing orprinting, causes the capsules on the reverse side to rupture. Thesolution of the color former released from the ruptured microcapsulesflows to the receiving sheet and on contact with the acidic mediumthereon forms a yellow to purple-colored image of good tinctorialstrength. It is, of course, obvious that variants of this mode ofapplication can be utilized, for example the receiving sheet in amanifold can alternatively be coated with the subject compounds and theacidic developing agent can be contained in microcapsules applied to thereverse side of the top sheet in the manifold; or the receiving sheetcan be coated with a mixture containing both the acidic developing agentand the microencapsulated color-former.

It has also been found that when the compounds of Formula I areintimately mixed with an acidic developer of the type generally employedin thermal papers, for example bisphenol A as described in U.S. Pat. No.3,539,375, that is, papers which produce a colored image when contactedwith a heated stylus or heated type, heating of the mixture produces acolored image of varying shades from yellow to purple, depending on theparticular compound of the invention employed. The ability of thecompounds of Formula I to form a deep color when heated in admixturewith an acidic developer such as bisphenol A makes them useful inthermal paper marking systems either where an original or a duplicatecopy is prepared by contacting the thermal paper with a heated stylus ora heated type in any of the methods generally known in the art.

The compounds of this invention which are soluble in water orlower-alkanols, for example the compounds of Formula I wherein R₃ istri-lower-alkylammonium-lower-alkyl can be incorporated in any of thecommercial hectographic or spirit reproducing copying systems such asdescribed in British Pat. No. 1,427,318, published Mar. 10, 1976. Insuch systems a transfer sheet coated on one side with a layer containingone or more water- or lower-alkanol-soluble color formers of Formula Iis placed with its coated surface against one surface of a master paperwhich is then typed, written or marked on, causing transfer of thecoating as a substantially colorless reverse image to the master paperat the points where the transfer sheet and master paper have beenpressed together. The master paper is then brought into contact with asuccession of sheets of paper moistened with a suitablespirit-reproducing fluid such as ethanol.

In accordance with the aforementioned process aspect of this invention,the above-described novel 1-R₁ -2-R₂ -3-[(R₃ O)(Z)methyl]-1H-indoles ofFormula I as well as certain known related compounds are obtained byreacting a R-phenylsulfonyl compound of Formula II with an alcohol ofFormula III in the presence of an alkali metal hydroxide or the alkalimetal salt of said alcohol at a temperature of from about 0°-100° C. forapproximately 10 minutes to 24 hours. The reaction is convenientlycarried out in the presence of potassium hydroxide and at about 20°-60°C. for approximately 1 to 20 hours employing an excess of the alcohol assolvent. The product thus obtained can be isolated by filtration if itis insoluble in the reaction medium or by dilution of the reactionmedium with a miscible solvent in which the product is insoluble, suchas water, a lower-alkanol, for example isopropyl alcohol, or a lowmolecular weight hydrocarbon, for example hexane, in order to effectprecipitation of the product. Alternatively, the reaction mixture can bepoured into water and the product extracted with an organic solvent suchas benzene or toluene followed by evaporation of the organic solventleaving the product as a residue. The product, once isolated, can bepurified by conventional means such as trituration or recrystallizationfrom a suitable solvent.

The 3-[(R-phenylsulfonyl)(Z)methyl]-1H-indoles of Formula II which arerequired as starting materials in the above-described process areobtained by reacting approximately equimolar amounts of an appropriate1-R₁ -2-R₂ -1H-indole, an appropriate aldehyde Z-CHO (Formula V) and anR-phenylsulfinic acid (R, R₁, R₂ and Z having the previously givenmeanings) in the presence of an acid catalyst such as hydrochloric acid,in a suitable solvent, for example N,N-dimethylformamide, or aloweralkanol such as methanol, ethanol or 2-propanol at a temperature ofabout 5°-150° C. for approximately 1 to 35 hours. The reaction isusually carried out in ethanol at about 5°-60° C. for approximately 1 to4 hours. The product thus obtained can be isolated by filtration if itis insoluble in the reaction medium or by the addition of a basicsubstance for example triethanolamine or ammonium hydroxide to effectprecipitation of the product. Alternatively, the reaction mixture can bepoured into water or a dilute aqueous base, for example ammoniumhydroxide, sodium hydroxide, sodium carbonate or sodium bicarbonate andthe product extracted with an organic solvent, such as benzene,chlorobenzene or toluene followed by evaporation of the organic solventleaving the product as a residue. The product, once isolated, can bepurified by conventional means such as trituration, recrystallization orslurrying in a suitable organic solvent.

The 1-R₁ -2-R₂ -1H-indoles as well as the aromatic or heterocyclicaldehydes of Formula V which are starting materials for preparing the3-[(R-phenylsulfonyl)(Z)methyl]-1H-indoles of Formula II constitutewell-known classes of compounds many of which are commercially availableor readily obtained by conventional syntheses well known in the art.

The R-phenylsulfinic acids which are also required as starting materialsfor the intermediates of Formula II likewise belong to an old andwell-known class of compounds. Sulfinic acids are known to be unstableand cannot be stored for long periods of time. Accordingly, in theabove-described reaction the sulfinic acid is generated in situ byacidifying an alkali metal R-phenylsulfinate which in turn is readilyobtained by conventional procedures, for example by reacting aR-phenylsulfonyl chloride with sodium sulfite and sodium bicarbonate inwater. The sodium R-phenylsulfinate is stable and can be stored untilneeded. The R-phenylsulfonyl chlorides are, of course, readily availablefrom the interaction of a R-phenylsulfonic acid or salt thereof withphosphorus oxychloride.

The compounds of Formula I hereinabove wherein R₁ is hydrogen, can alsobe prepared by reacting an indole of Formula IV containing an activehydrogen ##STR14## with an aldehyde of Formula V

    Z-CHO                                                      Formula V

and an alcohol of Formula III above (R₂ and Z having the previouslygiven meanings) in an excess of the latter as solvent and in thepresence of an alkali metal hydroxide or the alkali metal salt of thealcohol, at a temperature of from 0°-100° C. for approximately 0.5 hourto 5 days. Ordinarily, the reaction is carried out in the presence ofpotassium hydroxide at about 20°-30° C. for approximately 4 to 72 hours.The product so obtained can be isolated and purified as describedhereinabove.

The molecular structures of the compounds of this invention wereassigned on the basis of the modes of synthesis and study of theirinfrared and nuclear magnetic resonance spectra.

The following examples will further illustrate the invention without,however, limiting it thereto.

EXAMPLE 1

A. To a stirred mixture containing 175.0 ml. of ethyl alcohol, 27.5 ml.of concentrated hydrochloric acid, 30.4 g. of 86.4% sodiump-toluenesulfinate and 18.5 g. of p-(dimethylamino)benzaldehyde chilledto approximately 5° C. was slowly added 19.5 g. of 91.2%1-ethyl-2-methyl-1H-indole. The resulting mixture was stirredapproximately 3.5 hours at room temperature during which period thecolor changed from blue to yellow. The pH of the mixture was adjusted toapproximately 8 by the addition of 40.0 g. of triethanolamine and afterstirring approximately 20 minutes at room temperature the temperaturewas raised to and maintained at 55°-60° C. for approximately 20 minutes.After cooling to about 10° C. the resulting pink solid was collected byfiltration and washed with 100 ml. of cold ethyl alcohol. The solid wasthen suspended in a mixture of 350 ml. of water and 10 g. oftriethanolamine at room temperature for approximately 30 minutes,collected by filtration, washed successively with 150 ml. portions of 3%aqueous triethanolamine and water and dried under vacuum at 40° C. togive 42.2 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1-ethyl-2-methyl-1H-indolewhich softened at 155° C. and melted at 159°-161° C.

B. To a suspension of 4.5 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1-ethyl-2-methyl-1H-indolein 100 ml. of 2-propanol was added 1.5 g. of potassium hydroxide and themixture stirred 1 hour at room temperature. The resulting solid wascollected by filtration, washed successively with 2-propanol, water and2-propanol, and dried to give 2.6 g. of3-{[4-(dimethylamino)phenyl](2-propoxy)methyl}-1-ethyl-2-methyl-1H-indolewhich softened at 160° C., partially melted at 170°-172° C. and meltedcompletely at 179°-187° C. A toluene solution of this product whencontacted with acidic clay developed a bluish-red image and whencontacted with phenolic resin developed a purple image.

EXAMPLE 2

Following a procedure similar to that described in Example 1B butemploying 4.5 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1-ethyl-2-methyl-1H-indole,30 ml. of 2-butanol and 1.5 g. of potassium hydroxide, there wasobtained 2.6 g. of3-{[4-(dimethylamino)phenyl](2-butoxy)methyl}-1-ethyl-2-methyl-1H-indolewhich softened at 140° C., partially melted at 159° C. and meltedcompletely at 172°-174° C. A toluene solution of this product whencontacted with acidic clay developed a red image and when contacted withphenolic resin developed a purple image.

EXAMPLE 3

A. To a stirred mixture containing 5.0 ml. of concentrated hydrochloricacid, 35 ml. of ethyl alcohol, 9.6 g. of 55.6% sodium p-toluenesulfinateand 2.9 g. of 1,2-dimethyl-1H-indole was added 3.8 g. ofp-(dimethylamino)benzaldehyde. After stirring approximately 1 hour at55°-60° C. the reaction mixture was cooled to about 40° C. and thendiluted with 25 ml. of ethyl alcohol followed by 300 ml. of water and200 g. of ice. The resulting solid was collected by filtration andwashed with water. The product was suspended in 60 ml. of cold2-propanol containing sufficient ammonium hydroxide to maintain aslightly alkaline condition and the resulting suspension stirred forapproximately 45 minutes at 5°-10° C. The solid was then collected byfiltration, washed with 15 ml. of fresh 2-propanol and dried undervacuum at 45° C. to afford 8.9 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1,2-dimethyl-1H-indole,m.p. 179°-181° C.

B. Following a procedure similar to that described in Example 1B butemploying 3.0 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1,2-dimethyl-1H-indole,30 ml. of 2-propanol and 1.0 g. of potassium hydroxide there wasobtained 1.9 g. of3-{[4-(dimethylamino)phenyl](2-propoxy)methyl}-1,2-dimethyl-1H-indolewhich softened at 178° C. and melted at 190°-195° C. A toluene solutionof this product when contacted with acidic clay developed a red imageand when contacted with phenolic resin developed a violet image.

EXAMPLE 4

A. Following a procedure similar to that described in Example 3A butemploying 6.2 g. of 85.9% sodium p-toluenesulfinate, 4.5 g. of 94.4%1-ethyl-2-methyl-1H-indole and 2.8 g. of thiophene-2-carboxaldehyde,there was obtained 10.0 g. of3-[(4-methylphenylsulfonyl)(2-thienyl)methyl]-1-ethyl-2-methyl-1H-indole,m.p. 168°-169° C. (dec.)

B. Following a procedure similar to that described in Example 1B butemploying 5.0 g. of3-[(4-methylphenylsulfonyl)(2-thienyl)methyl]-1-ethyl-2-methyl-1H-indole,30 ml. of methanol and 2.0 g. of potassium hydroxide and stirring thereaction mixture 20 hours, there was obtained 2.6 g. of3-[(methoxy)(2-thienyl)methyl]-1-ethyl-2-methyl-1H-indole which softenedat 86° C. and melted at 89°-90° C. A toluene solution of this productwhen contacted with acidic clay or phenolic resin developed a yellowimage.

EXAMPLE 5

A. Following a procedure similar to that described in Example 1A butemploying 6.3 g. of 85% sodium p-toluenesulfinate, 2.2 g. of 98%1-methylpyrrole-2-carboxaldehyde and 3.8 g. of 94%1-ethyl-2-methyl-1H-indole, there was obtained 8.4 g. of3-[(1-methyl-2-pyrrolyl)(4-methylphenylsulfonyl)methyl]-1-ethyl-2-methyl-1H-indole,m.p. 180° C.

B. Following a procedure similar to that described in Example 1B butemploying 3.0 g. of3-[(1-methyl-2-pyrrolyl)(4-methylphenylsulfonyl)methyl]-1-ethyl-2-methyl-1H-indole,30 ml. of methanol and 1.0 g. of potassium hydroxide, there was obtained1.7 g. of3-[(methoxy)(1-methyl-2-pyrrolyl)methyl]-1-ethyl-2-methyl-1H-indolewhich softened at 125° C. and melted at 127°-129° C. A toluene solutionof this product when contacted with acidic clay or phenolic resindeveloped an orange image.

EXAMPLE 6

A. Following a procedure similar to that described in 3A but employing6.5 g. of 85.9% sodium p-toluenesulfinate, 4.6 g. of1-ethyl-2-methyl-1H-indole-3-carboxaldehyde and 3.8 g. of1-ethyl-2-methyl-1H-indole there was obtained 4.5 g. of3-[(1-ethyl-2-methyl-1H-indol-3-yl)(4-methylphenylsulfonyl)methyl]-1-ethyl-2-methyl-1H-indole,m.p. 146°-152° C.

B. Following a procedure similar to that described in Example 1B butemploying 5.0 g. of3-[(1-ethyl-2-methyl-1H-indol-3-yl)(4-methylphenylsulfonyl)methyl]-1-ethyl-2-methyl-1H-indole,50 ml. of methanol and 2 g. of potassium hydroxide there was obtained2.2 g. of3-[(1-ethyl-2-methyl-1H-indol-3-yl)(methoxy)methyl]-1-ethyl-2-methyl-1H-indolewhich softened at 94° C. and melted at 98°-108° C. A toluene solution ofthis product when contacted with acidic clay or phenolic resin developedan orange image.

EXAMPLE 7

To a mixture containing 5.0 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1-ethyl-2-methyl-1H-indoleand 35 ml. of t-butanol was added 1.5 g. of potassium hydroxide and theresulting mixture heated 3 hours at 45° C. and then 4 hours at 60° C.The reaction mixture was diluted with 30 ml. of water and the resultingsolid collected by filtration; washed successively with water, hexaneand 2-propanol and dried to give 2.6 g. of pale yellow solid.Recrystallization from acetone-ethanol afforded 1.1 g. ofbis-{[4-(dimethylamino)phenyl](1-ethyl-2-methyl-1H-indol-3-yl)methyl}etherwhich softened at 198° C., partially melted at 222°-225° C. and meltedcompletely at 275° C. A toluene solution of this product when contactedwith acidic clay developed a bluish-red image and when contacted withphenolic resin developed a purple image.

EXAMPLE 8

A. Following a procedure similar to that described in Example 3A butemploying 6.5 g. of 81.9% sodium p-toluenesulfinate, 5.1 g. of 95%2-phenyl-1H-indole and 3.8 g. of p-(dimethylamino)benzaldehyde, therewas obtained 10.3 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-2-phenyl-1H-indole,m.p. 185.5°-188° C.

B. To a mixture containing 3.0 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-2-phenyl-1H-indoleand 100 ml. of methanol was added 1.0 g. of potassium hydroxide. Afterstirring 3 hours at room temperature the reaction mixture was filteredto remove a small amount of insoluble material and the filtrate waspoured into 500 ml. of water. The resulting precipitate was collected,washed with water and dried to give 2.2 g. of3-{[4-(dimethylamino)phenyl](methoxy)methyl}-2-phenyl-1H-indole, m.p.80°-118° C. A toluene solution of this product when contacted withacidic clay developed a violet image and when contacted with phenolicresin developed a chocolate brown image.

EXAMPLE 9

To a mixture containing 4.5 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1-ethyl-2-methyl-1H-indoleand 30 ml. of n-butanol was added 1.5 g. of potassium hydroxide. Afterstirring two hours at room temperature, the reaction mixture was pouredinto 1 liter of water and the product extracted with toluene. Thetoluene solution was washed with water and saturated aqueous sodiumchloride and then evaporated to dryness under vacuum to give 3 g. of3-{(n-butoxy)[4-(dimethylamino)phenyl]methyl}-1-ethyl-2-methyl-1H-indoleas a light tan oil. A toluene solution of this product when contactedwith acidic clay developed a bluish-red image and when contacted withphenolic resin developed a violet image.

EXAMPLE 10

A. Following a procedure similar to that described in Example 3A butemploying 6.5 g. of 81.9% sodium p-toluenesulfinate, 6.3 g. of 95%4-(benzylethylamino)benzaldehyde and 3.8 g. of 86.1%1-ethyl-2-methyl-1H-indole, there was obtained 15.3 g. of3-{[4-(benzylethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1-ethyl-2-methyl-1H-indoleas a gray tar-like product.

B. Following a procedure similar to that described in Example 9 butemploying 4.0 g. of3-{[4-(benzylethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1-ethyl-2-methyl-1H-indole,100 ml. of methanol and 1 g. of potassium hydroxide and stirring thereaction mixture 3 hours there was obtained 2.6 g. of3-{[4-(benzylethylamino)phenyl](methoxy)methyl}-1-ethyl-2-methyl-1H-indoleas a brown oil. A toluene solution of this product when contacted withacidic clay developed a bluish-red image and when contacted withphenolic resin developed a purple image.

EXAMPLE 11

A. Following a procedure similar to that described in Example 3A butemploying 6.5 g. of 81.9% sodium p-toluenesulfinate, 2.4 g. of furfuraland 3.8 g. of 86.1% of 1-ethyl-2-methyl-1H-indole there was obtained 4.5g. of3-[(2-furyl)(4-methylphenylsulfonyl)methyl]-1-ethyl-2-methyl-1H-indole,m.p. 144°-146° C.

B. Following a procedure similar to that described in Example 9 butemploying 5.0 g. of3-[(2-furyl)(4-methylphenylsulfonyl)methyl]-1-ethyl-2-methyl-1H-indole,75 ml. of methanol and 2.0 g. of potassium hydroxide and stirring thereaction mixture 4 hours, there was obtained following trituration ofthe product with hexane and 2-propanol approximately 0.1 g. of3-[(2-furyl)(methoxy)methyl]-1-ethyl-2-methyl-1H-indole as a tan solid,m.p. 165° C. (dec.). A toluene solution of this product when contactedwith acidic clay or phenolic resin developed a yellow image.

EXAMPLE 12

Following a procedure similar to that described in Example 9 butemploying 8.92 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1-ethyl-2-methyl-1H-indole,80 ml. of methanol and 3.0 g. of potassium hydroxide and heating thereaction mixture at 45° C. for 20 hours, there was obtained followingtrituration of the product with hexane 4.28 g. of3-{[4-(dimethylamino)phenyl](methoxy)methyl}-1-ethyl-2-methyl-1H-indoleas a pale pink solid, m.p. 76°-83° C. A toluene solution of this productwhen contacted with acidic clay or phenolic resin developed a bluish-redimage.

EXAMPLE 13

Following a procedure similar to that described in Example 9 butemploying 3.0 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1,2-dimethyl-1H-indole,30 ml. of n-hexanol and 1.0 g. of potassium hydroxide, stirring thereaction mixture 18 hours and removing excess n-hexanol by vacuumdistillation (temperature maintained below 50° C.), there was obtained2.3 g. of3-{[4-(dimethylamino)phenyl](n-hexyloxy)methyl}-1,2-dimethyl-1H-indole.A sample crystallized from hexane softened at 125° C. and melted at168°-206° C. A toluene solution of this product when contacted withacidic clay or phenolic resin developed a bluish-red image.

EXAMPLE 14

To a mixture containing 6.8 g. of3-{[4-(dimethylamino)phenyl](4-methylphenylsulfonyl)methyl}-1-ethyl-2-methyl-1H-indoleand 35 ml. of benzyl alcohol was added 2.0 g. of potassium hydroxide.After stirring 2 hours at room temperature the reaction mixture waspoured into water and the product extracted with toluene. The tolueneextracts were steam distilled to remove excess benzyl alcohol. The gummyresidue was dissolved in 200 ml. of acetone and the resulting solutionadded slowly to 1 liter of 1% aqueous ammonia. The resulting solid wascollected, washed with water and dried to give 3.4 g. of3-{(benzyloxy)[4-(dimethylamino)phenyl]methyl}-1-ethyl-2-methyl-1H-indole,m.p. 53°-77° C. A toluene solution of this product when contacted withacidic clay develped a red image and when contacted with phenolic resindeveloped a violet image.

EXAMPLE 15

A mixture containing 6.5 g. of 2-methyl-1H-indole, 6.0 g. ofp-tolylaldehyde and 3.0 g. of potassium hydroxide in 50 ml. of methanolwas stirred 44 hours at room temperature. The solid which formed wascollected by filtration and washed with 2-propanol. The product was thenslurried in 300 ml. of 50% aqueous methanol, filtered and washed withmethanol to give 6.4 g. of3-[(methoxy)(p-tolyl)methyl]-2-methyl-1H-indole, m.p. 156°-159° C. Atoluene solution of this product when contacted with acidic clay orphenolic resin developed a yellow image.

EXAMPLE 16

Following a procedure similar to that described in Example 15 butemploying 5.9 g. of indole, 6.0 g. of p-tolylaldehyde, 40 ml. ofmethanol and 3.0 g. of potassium hydroxide and stirring the reactionmixture 1 day, there was obtained 4.51 g. of3-[(methoxy)(p-tolyl)methyl]-1H-indole, m.p. 96°-98° C. A toluenesolution of this product when contacted with acidic clay or phenolicresin developed a yellow image.

EXAMPLE 17

Following a procedure similar to that described in Example 15 butemploying 6.5 g. of 2-methyl-1H-indole, 5.6 g. of2-thiophenecarboxyaldehyde, 50 ml. of methanol and 3.0 g. of potassiumhydroxide and stirring the reaction mixture 24 hours, there was obtained9.45 g. of 3-[(methoxy)(2-thienyl)methyl]-2-methyl-1H-indole, m.p.116°-122° C. A toluene solution of this product when contacted withacidic clay or phenolic resin developed a yellow image.

EXAMPLE 18

Following a procedure similar to that described in Example 15 butemploying 6.0 g. of indole, 5.8 g. of 2-thiophenecarboxaldehyde, 50 ml.of methanol and 3.0 g. of potassium hydroxide and stirring the reactionmixture 4 hours, there was obtained 2.6 g. of3-[(methoxy)(2-thienyl)methyl]-1H-indole, m.p. 107°-112° C. A toluenesolution of this product when contacted with acidic clay developed apinkish-yellow image and when contacted with phenolic resin developed ayellow image.

EXAMPLE 19

Following a procedure similar to that described in Example 15 butemploying 6.5 g. of 2-methyl-1H-indole, 9.2 g. of 4-phenylbenzaldehyde,100 ml. of methanol and 3.0 g. of potassium hydroxide and stirring thereaction mixture 2 days, there was obtained 4.6 g. of3-[(4-biphenylyl)(methoxy)methyl]-2-methyl-1H-indole, m.p. 170°-173° C.A toluene solution of this product when contacted with acidic claydeveloped a yellow image.

EXAMPLE 20

Following a procedure similar to that described in Example 15 butemploying 6.5 g. of 2-methyl-1H-indole, 6.8 g. of p-anisaldehyde, 60 ml.of methanol and 3.0 g. of potassium hydroxide and stirring the reactionmixture 66 hours, there was obtained 12.0 g. of3-[(4-methoxyphenyl)(methoxy)methyl]-2-methyl-1H-indole, m.p.150.5°-153.8° C. A toluene solution of this product when contacted withacidic clay developed an orange-yellow image.

EXAMPLE 21

Following a procedure similar to that described in Example 15 butemploying 6.5 g. of 2-methyl-1H-indole, 8.3 g. of3,4-dimethoxybenzaldehyde, 50 ml. of methanol and 3.0 g. of potassiumhydroxide and stirring the reaction mixture 20 hours, there was obtained7.1 g. of 3-[(3,4-dimethoxyphenyl)(methoxy)methyl]-2-methyl-1H-indole,m.p. 148°-149° C. A toluene solution of the product when contacted withacidic clay or phenolic resin developed an orange-yellow image.

EXAMPLE 22

Following a procedure similar to that described in Example 15 butemploying 6.5 g. of 2-methyl-1H-indole, 7.2 g. of p-chlorobenzaldehyde,50 ml. of methanol and 3.0 g. of potassium hydroxide and stirring thereaction mixture 1 day, there was obtained 1.1 g. of3-[(4-chlorophenyl)(methoxy)methyl]-2-methyl-1H-indole, m.p. 98°-99.5°C. A toluene solution of this product when contacted with acidic claydeveloped a yellow image.

EXAMPLE 23

Following a procedure similar to that described in Example 15 butemploying 6.5 g. of 2-methyl-1H-indole, 5.3 g. of benzaldehyde, 25 ml.of methanol and 3.0 g. of potassium hydroxide, and stirring the reactionmixture 7 hours, there was obtained 7.56 g. of3-[(phenyl)(methoxy)methyl]-2-methyl-1H-indole, m.p. 251°-253° C. Atoluene solution of the product when contacted with acidic clay orphenolic resin developed an orange image.

EXAMPLE 24

A. Following a procedure similar to that described in Example 15 butemploying 6.5 g. of 2-methyl-1H-indole, 5.3 g. of benzaldehyde, 25 ml.of 2-(dimethylamino)ethanol and 3.0 g. of potassium hydroxide andstirring the reaction mixture 41 hours, there was obtained 6.34 g. of3-{[2-(dimethylamino)ethoxy](phenyl)methyl}-2-methyl-1H-indole, m.p.134.5°-135° C. A toluene solution of this product when contacted withacidic clay developed a yellow image.

B. Stirring for 0.5 hour a mixture containing 1.0 g. of the product ofpart A above, 1 ml. of methyl iodide, 50 ml. of chlorobenzene and 50 ml.of toluene; collection of the solid produced; washing with toluene anddrying, afforded 1.1 g. of the corresponding methiodide, m.p. 113°-130°C.

EXAMPLE 25

To a solution containing 3.2 g. of 2-methyl-1H-indole and 3.0 g. of4-(dimethylamino)benzaldehyde in 50 ml. of methanol at 5° C. was added1.5 g. of potassium hydroxide. The resulting mixture was then stirred 5days at room temperature and the solid which precipitated was collectedand washed with 2-propanol to give 1.4 g. of3-{[4-(dimethylamino)phenyl](methoxy)methyl}-2-methyl-1H-indole, m.p.172°-177° C. A toluene solution of this product when contacted withacidic clay or phenolic resin developed a deep red image.

EXAMPLE 26

Following a procedure similar to that described in Example 25 butemploying 6.5 g. of 2-methyl-1H-indole, 5.5 g. of2-pyridinecarboxaldehyde, 50 ml. of methanol and 3.0 g. of potassiumhydroxide, and stirring the reaction mixture 4 hours at room temperaturethere was obtained 10.6 g. of3-[(methoxy)(2-pyridyl)methyl]-2-methyl-1H-indole, m.p. 174°-177° C.When contacted with silica gel, this product developed an orange-pinkimage.

EXAMPLE 27

Following a procedure similar to that described in Example 25, butemploying 6.5 g. of 2-methyl-1H-indole, 5.0 g. of furfural, 50 ml. ofmethanol and 3.0 g. of potassium hydroxide, and stirring the reactionmixture 2 hours at room temperature there was obtained 5.0 g. of3-[(2-furyl)(methoxy)methyl]-2-methyl-1H-indole, m.p. 119°-121° C. Atoluene solution of this product when contacted with acidic clay orphenolic resin developed a yellow image.

EXAMPLE 28

A mixture containing 13.0 g. of 2-methyl-1H-indole, 17.5 g. of3,4-dichlorobenzaldehyde, 100 ml. of methanol and 5 g. of potassiumhydroxide was stirred 3 days at room temperature. The reaction mixturewas diluted with 10 ml. of water and the resulting solid was collectedby filtration, washed with 2-propanol and hexane and then dried.Recrystallization from 2-propanol-hexane afforded 7.7 g. of3-[(3,4-dichlorophenyl)(methoxy)methyl]-2-methyl-1H-indole, m.p.118°-119° C. A toluene solution of the product contacted with acidicclay or phenolic resin developed a greenish-yellow image.

EXAMPLE 29

To a solution containing 6.5 g. of 2-methyl-1H-indole, 7.6 g. ofm-nitrobenzaldehyde, in 100 ml. of methanol was added 3.0 g. ofpotassium hydroxide. After stirring 3 days at room temperature thereaction mixture was poured into 400 ml. of water and the gummy materialwhich separated was extracted with toluene. The toluene solution waswashed with water and saturated sodium chloride solution and thenevaporated to dryness under vacuum. The residue was triturated with 200ml. of hexane followed by 100 ml. of 2-propanol to give 4.2 g. of3-[(methoxy)(3-nitrophenyl)methyl]-2-methyl-1H-indole, m.p. 134°-143.5°C. A toluene solution of this product when contacted with acidic clay orphenolic resin developed a yellow image.

EXAMPLE 30

Following a procedure similar to that described in Example 29 butemploying 5.9 g. of indole, 6.8 g. of p-anisaldehyde, 50 ml. of methanoland 3.0 g. of potassium hydroxide and stirring the reaction mixture forone day, there was obtained 11.4 g. of3-[(methoxy)(4-methoxyphenyl)methyl]-1H-indole as a pale yellow oil. Atoluene solution of this product when contacted with acidic claydeveloped an orange red image and when contacted with phenolic resindeveloped an orange-yellow image.

EXAMPLE 31

Following a procedure similar to that described in Example 29 butemploying 6.5 g. of 2-methyl-1H-indole, 6.8 g. of o-anisaldehyde, 50 ml.of methanol and 3.0 g. of potassium hydroxide, and stirring the reactionmixture 2 days, there was obtained 3.4 g. of3-[(methoxy)(2-methoxyphenyl)methyl]-2-methyl-1H-indole, m.p. 121°-128°C. A toluene solution of this product when contacted with acidic claydeveloped an orange-yellow image and when contacted with phenolic resindeveloped a yellow image.

EXAMPLE 32

Following a procedure similar to that described in Example 29 butemploying 3.3 g. of 2-methyl-1H-indole, 5.6 g. of9-ethyl-3-carbazolecarboxaldehyde, 50 ml. of methanol and 2 g. ofpotassium hydroxide and stirring the reaction mixture 3 days, there wasobtained 6.2 g. of3-[(9-ethylcarbazol-3-yl)(methoxy)methyl]-2-methyl-1H-indole as a browngummy material. A toluene solution of this product when contacted withacidic clay or phenolic resin developed a pink-red image.

EXAMPLE 33

A. Following a procedure similar to that described in Example 29 butemploying 6.5 g. of 2-methyl-1H-indole, 6.5 g. of p-anisaldehyde, 20 ml.of 2-(dimethylamino)ethanol and 3.0 g. of potassium hydroxide andstirring the reaction mixture 1 day, there was obtained 6.4 g. of3-{[2-(dimethylamino)ethoxy](4-methoxyphenyl)methyl}-2-methyl-1H-indole,m.p. 84°-88° C. A toluene solution of this product when contacted withacidic clay or phenolic resin developed a yellow image.

B. Stirring for 0.5 hour a mixture containing 1.5 g. of the product ofpart A above, 1 ml. of methyl iodide and 30 ml. of toluene; collectingthe solid produced and washing with toluene afforded 0.95 g. of thecorresponding methiodide, m.p. 144°-151° C.

EXAMPLE 34

A mixture containing 6.5 g. of 2-methyl-1H-indole, 6.5 g. ofp-anisaldehyde, 20 g. of 4-methoxybenzyl alcohol and 3.0 g. of potassiumhydroxide was stirred 24 hours at room temperature. The reaction mixturewas diluted with 50 ml. of hexane and 50 ml. of 2-propanol and theresulting solid was collected, washed with 2-propanol and dried to give0.7 g. of3-[(4-methoxybenzyloxy)(4-methoxyphenyl)methyl]-2-methyl-1H-indole,m.p. >300° C. A toluene solution of this product when contacted withacidic clay or phenolic resin developed a yellow image.

EXAMPLE 35

Following a procedure similar to that described in Example 34 butemploying 6.5 g. of 2-methyl-1H-indole, 6.5 g. of p-anisaldehyde, 20 g.of n-butanol and 3.0 g. of potassium hydroxide, and stirring thereaction mixture 24 hours at room temperature there was obtained 12.4 g.of 3-[(n-butoxy)(4-methoxyphenyl)methyl]-2-methyl-1H-indole, m.p.89°-91° C. A toluene solution of this product when contacted with acidicclay or phenolic resin developed a yellow image.

EXAMPLE 36

Following a procedure similar to that described in Example 34 butemploying 6.5 g. of 2-methyl-1H-indole, 6.5 g. of p-anisaldehyde, 30 g.of benzyl alcohol and 3.0 g. of potassium hydroxide, and stirring thereaction mixture 2 days at room temperature there was obtained 12.9 g.of 3-[(benzyloxy)(4-methoxyphenyl)methyl]-2-methyl-1H-indole, m.p.118°-121° C. A toluene solution of this product when contacted withacidic clay or phenolic resin developed a yellow image.

EXAMPLE 37

Following a procedure similar to that described in Example 34 butemploying 6.5 g. of 2-methyl-1H-indole, 5.6 g. of2-thiophenecarboxaldehyde, 20 ml. of benzyl alcohol and 3.0 g. ofpotassium hydroxide, and stirring the reaction mixture 40 hours at roomtemperature, there was obtained 3.21 g. of3-[(benzyloxy)(2-thienyl)methyl]-2-methyl-1H-indole, m.p. >300° C. Atoluene solution of this product when contacted with acidic clay orphenolic resin developed a yellow image.

EXAMPLE 38

Following a procedure similar to that described in Example 34 butemploying 6.5 g. of 2-methyl-1H-indole, 15.6 g. of2-thiophenecarboxaldehyde, 20 ml. of n-butanol and 3.0 g. of potassiumhydroxide and stirring the reaction mixture 16 hours at room temperaturethere was obtained 5.76 g. of3-[(n-butoxy)(2-thienyl)methyl]-2-methyl-1H-indole, m.p. 253.5°-255° C.A toluene solution of this product when contacted with acidic clay orphenolic resin developed a yellow image.

EXAMPLE 39

A mixture containing 6.5 g. of 2-methyl-1H-indole, 7.8 g. of1-naphthaldehyde, 35 ml. of methanol and 3.0 g. of potassium hydroxidewas stirred 4 days at room temperature. The reaction mixture was pouredinto 400 ml. of water and the aqueous solution was decanted from theresulting gummy precipitate. The latter was washed with hexane and thenevaporated to dryness under vacuum to afford 10.2 g. of3-[(methoxy)(1-naphthyl)methyl]-2-methyl-1H-indole, as a brown oil. Atoluene solution of this product when contacted with acidic clay orphenolic resin developed a yellow image.

EXAMPLE 40

A mixture containing 6.5 g. of 2-methyl-1H-indole, 6.8 g. ofp-anisaldehyde, 60 ml. of 2-propanol and 3.0 g. of potassium hydroxidewas stirred 3 days at room temperature. The product which separated fromthe reaction mixture as a gum was crystallized from 2-propanol to give afirst crop of 1.3 g. of yellow solid, m.p. 153.5°-160° C. A toluenesolution of this product when contacted with acidic clay developed ayellow image. Dilution of the filtrate with water afforded a secondcrop, m.p. 148°-151° C. and a third crop, m.p. 125°-130° C. Nuclearmagnetic resonance spectral analysis of the first and third cropsindicated each to be a mixture of3-[(4-methoxyphenyl)(2-propoxy)methyl]-2-methyl-1H-indole (I) and3-[(4-methoxyphenyl)(2-methyl-1H-indol-3-yl)methyl]-2-methyl-1H-indole(II). The first crop contained 16% I and 84% II and the third cropcontained 35% I and 65% II.

It is contemplated that by following procedures similar to thosedescribed in the foregoing examples but employing the appropriate 1-R₁-2-R₂ -3-[(R-phenylsulfonyl)(Z)methyl]-1H-indole and the appropriatealcohol R₃ OH there will be obtained the 1-R₁ -2-R₂ -3-[(R₃O)(Z)methyl]-1H-indoles of Formula I, Examples 41-50 presented in TableA hereinbelow.

                                      TABLE A                                     __________________________________________________________________________    1-R.sub.1 --2-R.sub.2 --3-[(R.sub.3 O)(Z)methyl]1H--indoles of Formula I      Ex.                                                                              R.sub.1                                                                            R.sub.2                                                                           R.sub.3      Z                                                    __________________________________________________________________________    41 C.sub.2 H.sub.5                                                                    CH.sub.3                                                                          C.sub.8 H.sub.17                                                                           4-(CH.sub.3).sub.2 N--C.sub.6 H.sub.4                42 n-C.sub.4 H.sub.9                                                                  H   CH.sub.3     4-(n-C.sub.4 H.sub.9).sub.2 N--C.sub.6 H.sub.3       43 C.sub.2 H.sub.5                                                                    CH.sub.3                                                                          CH.sub.3     2-Cl--4-(CH.sub.3).sub.2 N--C.sub.6 H.sub.3          44 C.sub.2 H.sub.5                                                                    CH.sub.3                                                                          CH.sub.3     2,4-[(CH.sub.3).sub.2 N].sub.2 --C.sub.6                                      H.sub.3                                              45 CH.sub.3                                                                           CH.sub.3                                                                          4-CH.sub.3 --C.sub.6 H.sub.4                                                               2-C.sub.2 H.sub.5 O--4-(C.sub.2 H.sub.5).sub.2                                N--C.sub.6 H.sub.3                                   46 H    CH.sub.3                                                                          C.sub.2 H.sub.5                                                                            2-CH.sub.3 --4-(CH.sub.3).sub.2 N--C.sub.6                                    H.sub.3                                              47 H    H   3,4-(CH.sub.3 O).sub.2 --C.sub.6 H.sub.3 CH.sub.2                                          4-(CH.sub.3).sub.2 N--C.sub.6 H.sub.4                48 C.sub.2 H.sub.5                                                                    CH.sub.3                                                                          4-(C.sub.2 H.sub. 5).sub.2 N--(CH.sub.2).sub.4 --                                          4-(CH.sub.3).sub.2 N--C.sub.6 H.sub.4                49 CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3     2-naphthyl                                           50 CH.sub.3                                                                           C.sub.6 H.sub.5                                                                   CH.sub.3     2-F--4-(CH.sub.3).sub.2 N--C.sub.6 H.sub.3           __________________________________________________________________________

EXAMPLE 51

The color former of Example 20 was microencapsulated and applied to acarbonless duplicating transfer sheet as follows: a solution prepared bydissolving 0.73 g. of the color former in 30 g. of isopropylbiphenyl at95° C. and a solution prepared by slowly dissolving 2.5 g. ofcarboxymethylcellulose in 100 ml. of distilled water were mixed andemulsified by rapid stirring at 50° C. The desired particle size (1-2microns) was checked by microscope. A solution prepared by dissolving7.5 g. of pigskin gelatin in 60 ml. of distilled water at 50° C.followed by stirring approximately one hour at 50° C. was then added tothe stirred emulsion and the pH was adjusted to 6.5 with 10% aqueoussodium hydroxide with rapid stirring. Following the gradual addition of335 ml. of distilled water at 50° C. the pH was adjusted to 4.5 with 10%aqueous acetic acid with continued rapid stirring. After five minutesthe mixture was cooled to 15° C. and 5 ml. of 25% aqueous glutaraldehydewas added dropwise while rapid stirring was continued an additional 15minutes. After stirring more slowly overnight the weight of themicrocapsule dispersion was adjusted to 560 g. with distilled water togive a color former concentration of approximately 0.13%. Whitetypewriter paper sheets (transfer sheets) were coated with thisdispersion at a film thickness of 0.0015 inch and air-dried. The coatedside of a transfer sheet was placed in contact with a receiving sheetcoated with either phenolic resin or acidic clay. Typing on the transfersheet produced a yellow duplicate typewritten image on the receivingsheet.

EXAMPLE 52

The color former of Example 12 was microencapsulated and applied to acarbonless duplicating transfer sheet as follows: A solution prepared bydissolving 1.46 g. of the color former in 60 g. of dibutyl phthalate at100° C. then cooling to 50° C. and a solution prepared by slowlydissolving 5 g. of carboxymethylcellulose in 200 ml. of distilled waterwere mixed and emulsified by rapid stirring. The desired particle size(5 microns) was checked by microscope. A solution prepared by dissolving15 g. of pigskin gelatin in 120 ml. of distilled water at 50° C.followed by stirring 1 hour at 50° C. was then added to the stirredemulsion and the pH was adjusted to 6.5 with 10% aqueous sodiumhydroxide with rapid stirring. Following the gradual addition of 670 ml.of water at 50° C. the pH was adjusted to 4.5 with 10% aqueous aceticacid with continued rapid stirring. After 5 minutes the mixture wascooled to 15° C. and 10 ml. of 25% aqueous glutaraldehyde was addeddropwise while rapid stirring was continued an additional 15 minutes.After stirring more slowly overnight, the weight of the microcapsuledispersion was adjusted to 1120 g. with distilled water to give a colorformer concentration of approximately 0.13%. White typewriter papersheets (transfer sheets) were coated with this dispersion at a filmthickness of 0.0015 inches and air-dried. The coated side of a transfersheet was placed in contact with a receiving sheet coated with eitherphenolic resin or acidic clay. Typing on the transfer sheet produced aviolet duplicate typewritten image on the receiving sheet.

EXAMPLE 53

The color formers of Examples 12 and 25 were incorporated in thermalpapers essentially as described in U.S. Pat. No. 3,539,375. Polyvinylalcohol dispersions of the color formers of Examples 12 and 25 wereprepared by shaking 1 hour on a paint shaker a mixture containing 2.0 g.of the color former, 3.7 g. of water, 8.6 g. of 10% aqueous polyvinylalcohol and 10 ml. of zirconium grinding beads. A polyvinyl alcoholdispersion of bisphenol A was prepared by shaking a mixture containing9.8 g. of bisphenol A, 18.2 g. of water, 42 g. of 10% aqueous polyvinylalcohol and 70 ml. of zirconium grinding beads. The coating mixture wasmade by combining and thoroughly mixing 2.1 g. of the polyvinyl alcoholdispersion of the color former with 47.9 g. of the polyvinyl alcoholdispersion of bisphenol A. The coating mixture was applied at athickness of 0.0015 inch to white paper sheets and the sheets were driedat room temperature. Contacting the coated sheets with a heated stylusat temperatures between 100° C. and 160° C. produced a violet to purpleimage on the sheet coated with the color former of Example 12 and ared-violet to blue-violet image on the sheet coated with the colorformer of Example 25.

We claim:
 1. A compound having the formula ##STR15## wherein: R₁ ishydrogen or lower-alkyl;R₂ is hydrogen, lower-alkyl or phenyl; R₃ isdi-lower-alkylamino-lower-alkyl or tri-lower-alkylammonium-lower-alkyl,and Z is phenyl, tolyl or lower-alkoxyphenyl. 2.3-{[2-(Dimethylamino)ethoxy](4-methoxyphenyl)methyl}-2-methyl-1H-indoleaccording to claim 1.